title: Assembly of surface-confined homochiral helicates: chiral discrimination of DOPA and unidirectional charge transfer.
abstract: Surface-confined double-helical polymers are generated by dynamic covalent assembly with preservation of chirality, metal coordination environment, and oxidation state of the precursor complexes. This one-step procedure involves both in solution and solution-to-surface assembly and resulted in chiral interfaces where pairs of ligands are wrapped around arrays of metal ions. In-plane XRD experiments revealed the formation of a highly ordered structure along the substrate surface. The chirality of the surfaces is expressed by the selective recognition of 3,4-dihydroxyphenylalanine (DOPA). The CD measurements show a response of the Δ-polymer-modified quartz substrates toward D-DOPA, whereas no change was observed after treatment with L-DOPA. These coordination-based interfaces assembled on metal-oxide substrates in combination with a redox-probe, [Os(bpy)3](PF6)2, in solution can resemble the behavior of a rectifier.
authors.affiliation: Department of Organic Chemistry, The Weizmann Institute of Science , 76100 Rehovot, Israel .
authors.forename: Revital
authors.initials: R
authors.lastname: Kaminker
authors.forename: Xavier
authors.initials: X
authors.lastname: de Hatten
authors.forename: Michal
authors.initials: M
authors.lastname: Lahav
authors.forename: Fabio
authors.initials: F
authors.lastname: Lupo
authors.forename: Antonino
authors.initials: A
authors.lastname: Gulino
authors.forename: Guennadi
authors.initials: G
authors.lastname: Evmenenko
authors.forename: Pulak
authors.initials: P
authors.lastname: Dutta
authors.forename: Colm
authors.initials: C
authors.lastname: Browne
authors.forename: Jonathan R
authors.initials: JR
authors.lastname: Nitschke
authors.forename: Milko E
authors.initials: ME
authors.lastname: van der Boom
mesh_terms: D056831:Coordination Complexes / Q000737:chemistry; D004295:Dihydroxyphenylalanine / Q000737:chemistry* / Q000302:isolation & purification; D007980:Levodopa / Q000737:chemistry / Q000302:isolation & purification; D008670:Metals / Q000737:chemistry; D008958:Models, Molecular; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010087:Oxides / Q000737:chemistry; D011108:Polymers / Q000737:chemistry*; D013237:Stereoisomerism
chemical_list: D056831:Coordination Complexes; D008670:Metals; D010087:Oxides; D011108:Polymers; D007980:Levodopa; D004295:Dihydroxyphenylalanine